Photographic element containing a trisazo dye



Patented June 1942 UNITED STATE PAT ENT 2,286,714

PIiOTOGRAPHIO ELEMENT CONTAINING A v TBISAZO DYE Jonas John Chechak, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing.

14 Claims.

Application March-22,1941, Serial No. 384,728

This invention relates to a photographic element andmore particularly to a single or multilayer photographic element wherein at least one of the layers is uniformly colored with a dye selected from the group of trisazo compoun having the general formula:

wherein R. and R each represents an aminonaphthol mono-sulfonic or di-sulfonic acid nucleus such as an H acid, 28" acid or S"-acid nucleus, and R1 and R2 each represents a benzene or a naphthalene nucleus. The nuclei represented by R1 and R2 can be further substituted in the free positions, if desired, by one ormore monovalent substituents'selected from the -group including methyl, ethyl, propyl, butyl, methoxy, 1

ethoxy, propoxy, methoxymethyl, methoxyethyl, v chlorine, bromine, and the like atoms and groups of atoms.

2 It is well known in the photographic art that dyes used in photographic layers such as filter diffuse by introducing an eircessive number of sulfonic acid groups into the dye molecule. Thisfactis-well known in the dye artand I do not intend to include within the scope of my invention dyes containing an excess number of solubilizing groups which increase the diffusion tendency. In general, the dyes of the types described in my invention are satisfactory with not more than two sulfonic acid groupsin each of the end nuclei, but ma diffuse if they contain a'greeter dyes, antihalation dyes and image-forming dyes should remain fixed in the layers wherein they.

are incorporated. Many of the dyes proposed,

however, tend to migrate from one layer to another, while others are sufliciently non-diffusing,

, but have the disadvantage of being diilicult to in-' corporate because of limited solubility characteristics, or, if capable of ready incorporation, cannot be satisfactorily bleached or removed from the layers during the processing operations. Then, too, there is always the problem of obtaining dyes, which in addition to having desirable characteristics of' good solubility, non-diifusability, ease of bleaching, and the like, must also have satisfactory colorranges and have no adverse eilects on sensitized emulsions.

While it is in general truethat increase in molecular size of the dye molecule tends to decrease its solubility and hence its mobility in colloidal compositions, I have found, however, that a suitable dye for photographic layers must be chosen with some discrimination, in order to preserve the desirable values, and exclude those least desirable. Thus, I have found that the above described trisazo compounds of my'inven- 'tion are highly desirable coloring materials for photographic layers with none of. the disadvantages mentioned; They do not seriously desensitize emulsions in which they are incorporated and can be decolorized readily by suitable treatment of the photographic material wherein they are contained.

Furthermore, the dy provide image-forming dyes .for, color 'photog} raphy which have the proper spectral absorption ranges. Other objects will appear from the following description of my invention.

40 prepared by tetrazotizing diaminoazobenzenes, di-

es which I have described 0 number of sulfonic 8. id groups. It will be appreciated, therefore, t at my dye compounds. are

critically balanced between type and color of the compound, its ease of bleachin its solub tyjand its diffusion tendency. It is anobiect of my invention, therefore, to provide a photographic element having atzleest one layer containing a trisazo dye therein which does not diffuse through gelatin or which diflueee only slightly. A further object is to provide dyes suitable bleaching agent. Another object is to The trisazo compounds of my invention may be amino azonaphthalenes' or amino-phenyl-azo- I naphthylamines and coupling with twomolar equivalents of an aminonaphthol monoor disulfonic acid.. The amino-naphthol monoor di-sulfonic acid mayor may not be further substituted in the amino group by acyl, alkyl, aracyl,

arallryl, a'rylsulfonyl and the like groups.

Thefollowing examples. wh ch are illustrative only, indicate dyes which are ,suitable for use accordingtomy invention.

. Example 1 Theblue colored dye made by tetraaotizing 1 mole oi4-aminophenyl-1-(-azo-4') -(1' naphthylamine-6'-sulphonic acid) and coupling in an al- FICE which do not seriously desensitize emulsion layers. A still further object is to provide dyes for color' photograph which can be bleached readily in the presence of a silver image by the use of a kaline solution with 2 moles of 1,8-benzoylaminonaphthol-3,6-disulfonic acid (benzoyl-H-acid) and having the following probable'structure in the free state S 01H SOaH Example 2 The blue colored dye made by tetrazotizing 1 mole of 4,-4'-diaminoazobenzene and coupling with 2 moles of 1,8-aminonaphthol-2,4-disulfonic acid (28 acid) and having the following probable formula in the free state:

NH: OH O H s o ,fiIjmNOMN- ON=N Example 3 The blue dye made by tetrazotizing 1 mole of 4,4-diaminoazobenzene and coupling in an al- H NH:

SOaH

sensitive photographic layers, the dyes which I v have described may be used in a photographic material such as that described in Christensen kalinemedium with 2 moles of S-acid (1,8-aminonaphthol-4-sulfonic acid) and having the following probable structure in the free state:

NH; /O H O H NH:

S 0 111 S 0 IE Example 4 The reddish blue dye made by tetrazotizing 1 mole of 4,4'-diaminoazobenzene and coupling in alkaline medium with 2 moles of 2-amino-8- 'naphthol-G-sulfonic acid and having in the fre state the following probable structure:

OH I ENN=NON=NGN=N NH;

SOsH

Example 5 The blue dye made by tetrazotizing 1 mole of 4,4-diamino 2,5-dimethoxy-azobenzene and coupling in an alkaline medium with 2 moles of ZS-acid (1,8-aniinonaphthol-2A-disulfonic acid) and having in the free state the following probable formula:

NH, on OCH; OH NH:

HSO N=N- N=NON=N solH S 01H S 03H U. S. Patent No. 1,517,049, issued November 5,

1934. In the material described in the Christensen patent, ,the sensitive layers are uniformly colored a color complementary to that which they are designed to record. The blue-sensitive layer is colored yellow, the green-sensitive layer is colored magenta and the red-sensitive layer is colored blue-green. However, the dyes used according to my invention may also be incorporated in layers which are sensitized to any color. For example, the dyes proposed according to my invention, all of which are of bluish color may be incorporated in any or all desired layers of a multi-layer coating.

The sensitive compositions containing my dyes may be coated on transparent film supports such as a derivative of cellulose including cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate-propionate, cellulose acetate=butyrate, cellulose ether, and

the like, as well as on synthetic resin supports such as polyvinyl acetal, and opaque supports such as paper or cellulose derivatives mixed with opaque white pigments. They may be used in single layer or multi-layer coatings or in multilayer coatings on one or both sides of a support.

Dyes of the general structure which I have I described are practically non-difiusing in gelatin and have little or no adverse eflect on the sensitivity of the emulsion in which they are incorporated or on adjacent emulsion layers. They can be bleached in the presence of a silver or silver salt image with suitable bleaching solutions such as sodium stannite, the silver' salt image being converted to a silver image in the operation, and when used in filter layers, they can be discharged by the use of sodium. hydrosulfite or potassium permanganate and acid.

I claim: 1. A photographic element comprising a support having thereon a light-sensitive layer,- at

least one layer comprising gelatin and a dye havwherein R and R3 each represents a member selected from the group consisting of an aminonaphthol-monosulfonic acid nucleus, and an aminonaphthol-disulfonic acid nucleus, and R1 and R2 each represents a member selected from the group consisting of a benzene nucleus, and a naphthalene nucleus.

2. A photographic element comprising a support having thereon a light-sensitive layer, at

least one layer comprising gelatin and a dye having the general formula:

RN=NR1-N =NR2N=NRa' wherein R and R3 each represents a member selected from the group consisting of an aminonaphthol-monosulfonic acid nucleus, and an When used as image-fm'mingdyes in light aminonaphthol-disulfonic acid nucelus, and R and R2 each represents a benzene nucleus.

3. A photographic element comprising a support having thereon a light-sensitive layer. at

least one layer comprising gelatin and a dye having the general formula:

wherein R and R3 each represents a member selected from the group consisting of an aminonaphthol-monosulfonic acid nucleus, and an aminonaphthol-disulfonic acid nucleus, and R1 and R2 each represents a naphthalene nucleus.

. 5. A photographic-element comprising a support having thereon a light-sensitive layer, at

least one layer comprising gelatin and a dye having the general formula:

wherein R and R3 each represents a member selected from the group consisting of a 1,8-amino- ,naphthol-monosulfonic acid nucleus, and a 1,8-

aminonaphtholrdisulfonic acid nucleus, and R1 and R2 each represents a benzene nucleus.

6. A photographic element comprising a supp port having thereon a light-sensitive layer, at

least one layer comprising gelatin and a dye having the general formula:

wherein R1 and R2 each represents a benzene nucleus.

7. A photographic element comprising a support having thereon a light-sensitive layer, atv

least one layer comprising gelatin and a dye having the formula:

NH: 0 H OH NH: risoaqjnmo uownmsom 3H OaH 8. A gelatino-silver halide layer for .a dyebleaching process of color photography, miformly colored with a dye having the general formula:

wherein R. and R3 each represents a member selected from the group consisting of an amino- -naphtho1-monosulfonic acid nucleus, and an aminonaphthol-disulfonic acid nucleus, and R1 and R2 each represents a member selected from the group consisting of a benzene nucleus, and a naphthalene nucleus. 1 9. A gelatino-silver halide layer for a dyebleaching process of color photography, uniformly colored with a dye having the general wherein R and Rs each represents a memberselected from the group consisting of an amino- 1 naphthol-monosulfonic acid nucleus, and an aminonaphthol-disulfonic' acidnucleus, and R1 and R2 each represents a benzene nucleus.

10. A gelatino-silver halidelayer for a dye-:

{bleaching process of color photography. uniformly colored with a dye having the general:

wherein R and R3 each represents a member selected from the group consisting'of an aminonaphthol-monosulfonic acid nucleus, and an aminonaphthol-disulfonic acid nucleus, R1 represents a benzene nucleus, and R2 represents a naphthalene nucleus.

11. A gelatino-silver halide layer for a dyebleaching process of color photography, uniformly colored with a dye having the general formula:

wherein R and R3 each represents a member selected from the group consisting of an aminonaphthol-monosulfonic acid' nucleus, and an aminonaphthol-di'sulfonic acid nucleus, and R1 and R2 each represents a naphthalene nucleus.

' 12. A gelatino-silver halide layer for a dye bleaching process of color photography, uniformly colored with a'dye having the general formula:

wherein R and R3- each represents a member selected from the group consisting of a 1,8- aminonaphthol-monosulfonic acidnucleus, and a 1,8-aminonaphthol-disulfonic acid nucleus, and R1 and R2 each represents a benzene nucleus.

13. A gelatino-silver halidelayer for a dyebleaching process of color photography, uniformly colored with a dye having the general formula:

wherein R1 and R2 each represents a benzenenucleus. i

14. A- gelatino-silver halide layer for a dyebleaching process of color photography, 'uniformly colored with a dye having the formula:

NE: on o ,Hso N=NON=NON=N 80.11

i V J I l I 03H QaH onas JOHN 'crmonm' 

